32 C9ta08321a 240327 115333

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Emergence of rechargeable seawater batteries

Cite this: J. Mater. Chem. A, 2019, 7, S. T. Senthilkumar, a Wooseok Go,a Jinhyup Han,a Linh Pham Thi Thuy,a
22803 Koshal Kishor, a Yongil Kima and Youngsik Kim *ab
Published on 07 October 2019. Downloaded by KIT Library on 4/19/2021 4:06:14 PM.
New concepts or chemistry is an urgent requirement for rechargeable batteries to achieve a low-cost, user-
friendly nature with adequate energy densities and high levels of safety. Rechargeable seawater batteries
(SWBs) are a new electrochemical system for the storage of electrical energy that utilizes seawater, as an
infinite resource, as a source of the Na+ ion cathode. Seawater is a naturally available abundant
renewable resource that covers nearly 70% of the Earth's surface. This review provides an essential
comprehensive introduction to new rechargeable SWBs. First, we present details of seawater and then
the history of primary SWBs and rechargeable SWBs, and the structure and chemistry of rechargeable
SWBs. Next, we describe the research progress that has so far been made on various components of
SWBs, such as cathode current collectors, electrocatalysts, solid electrolyte, anodes, and non-aqueous
Received 31st July 2019
Accepted 26th September 2019
electrolyte, including the performance metrics reported in the literature. Moreover, some concepts of
modified rechargeable SWB design for desalination and CO2 reduction application are discussed. Lastly,
DOI: 10.1039/c9ta08321a
we provide our future outlook on the development of rechargeable SWBs and emphasize the main
rsc.li/materials-a practical issues with the hope of stimulating further research progress.
At present, rechargeable Li-ion batteries (LIBs) are the most

1. Introduction renowned electrochemical ESS owing to their characteristics of
Worldwide, renewable power technologies such as solar, wind, high-energy-density charge storage (250 kW h1) and cycle life,10
and tidal are considered potential alternatives to thermal and and these characteristics make them superior in portable
nuclear power technologies for producing clean green elec- devices, electronics, electric vehicles, and grid energy storage
tricity. Thermal power plants emit CO2 gas, which is the cause applications.9,11,12 However, LIBs are very costly (USD 250 per
of global warming,1–3 and nuclear power plants are based on kW h) and have safety issues, which are the main factors
highly radioactive materials that are highly hazardous to nature hindering their scale-up, especially in the grid energy storage
and all living organisms, including humans.4,5 Hence, most eld. The high-cost concern is due to the use of expensive
countries have already started to produce the maximum lithium and cobalt-based raw materials in LIBs for achieving the
amount of electricity from renewable power technologies by high-energy system. The element cobalt is not only expensive
reducing the number of thermal and nuclear power plants. but also toxic and has limited availability, like lithium.13 The
However, renewable power technologies have the drawback of safety problem of LIBs arises from their operation in low-ash-
an intermittent electricity supply. This intermittent nature point ammable organic electrolytes.14 Most importantly,
motivated us to deploy a suitable electrical energy storage compared with energy density, batteries should provide low
system (ESS) that can store a large amount of electricity cost, sustainability, and safety for their wide application; this
produced from renewable power technologies and transfer situation compelled researchers to seek an alternative
electricity on demand economically.3,6 An electrochemical ESS, rechargeable battery system for LIBs.
which can be chosen from among many ESSs, is a great solution It is recognized by battery experts that the use of earth-
for matching uctuating electricity supply with demand. abundant metals such as aluminum (Al), magnesium (Mg),
Generally, electrochemical ESSs can offer carbon-free electricity, sodium (Na), potassium (K), and calcium (Ca)-based materials
low maintenance, high round-trip efficiency, a long cycle life, in batteries15–21 would signicantly reduce their cost because, Al,
and exible power and energy features.2,3,7–9 Mg, Na, K, and Ca are more abundant and cheaper elements.
Nonetheless, seawater is an innite resource for the Na
element, which is the fourth most abundant element due to its
availability in the form of Na+ ions in seawater.22–24 The
concentration of Na+ ions in seawater is approximately 0.47 M;25
a
School of Energy and Chemical Engineering, Ulsan National Institute of Science and
Technology (UNIST), UNIST-gil 50, Ulsan 44919, Republic of Korea. E-mail: ykim@
thus, it can possibly act as an Na+ ion source, like the cathodes
unist.ac.kr
b
Energy Materials and Devices Lab, 4TOONE Corporation, UNIST-gil 50, Ulsan 44919,
used in rechargeable Na-ion batteries. With this motivation,
Republic of Korea recently, rechargeable seawater batteries (SWBs) have been
This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 22803–22825 | 22803
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Journal of Materials Chemistry A Review
developed that use seawater, as an unlimited resource, as Table 1 Composition of standard seawater28
a source of the Na+ ion cathode for electrical energy storage. In
Percentage of Concentration
this battery, an anode in a non-aqueous electrolyte is protected
Chemical ions total salt content (%) (ppm) g kg1
from the seawater cathode by an Na+ ion-conductive solid
electrolyte, which can block water molecules and ions other Cl (chloride) 55.0 19.345
than Na+ ions25–27 (a detailed discussion regarding the cell Na+ (sodium) 30.6 10.752
structure and their electrochemical reactions will be provided in SO42 (sulfate) 7.6 2.701
Mg2+ (magnesium) 3.7 1.195
the subsequent section). Ca2+ (calcium) 1.2 0.416
From our efforts, we hope that the utilization of abundant K+ (potassium) 1.1 0.390
seawater and its free natural availability will enable its HCO3 (bicarbonate) 0.4 0.145
application in large-scale ESSs with eco-friendly and price- Br (bromide) 0.2 0.066
BO32 (borate) 0.08 0.027
competitive features. Compared with LIBs, however, the

Sr2+ (strontium) 0.04 0.013
research on rechargeable SWBs is still in an embryonic stage F (uoride) 0.003 0.001
for commercialization. However, our general goal is to
develop rechargeable SWBs with price competitiveness in
terms of energy, power, cycle life, and compatibility in future
it must be emphasized that the concentration of dissolved salt
ESS applications. Therefore, several investigations are active
ions is not similar throughout the ocean; it differs from place to
concerning electrolytes and electrode materials for the anode
place, and is mainly controlled by the local weather (cold or
side, electrocatalysts and current collectors for the cathode
hot), environment, and rainfall rate.
side, and selective Na+ ion-conductive membranes (i.e. a solid
Moreover, the presence of dissolved salt ions in seawater
electrolyte). In this review article, we rst provide details on
supports a high ionic conductivity of approximately 50 mS cm1
seawater and then a comprehensive overview of conventional
(at 20 C). Thus, seawater has been considered as an electrolyte
primary seawater batteries (SWBs) and their comparison with
for several applications, such as water electrolysis29,31,32 and
rechargeable SWBs based on design and working principles.
electrochemical cells (for example: supercapacitors and
Subsequently, we summarize the current state of the art of
batteries).33–36 However, the conductivity of seawater varies
progress in rechargeable SWBs to understand research
depending on temperature and salinity.37–39 Generally, the pH of
approaches and the various performance metrics reported in
seawater is approximately 8.1, which shows that seawater is
the literature. Following this, we discuss modied recharge-
slightly more basic in nature than freshwater (pH ¼ 7). Like-
able SWBs for desalination and CO2 reduction applications.
wise, seawater not only contains dissolved salt ions but also
Lastly, we offer future perspectives on the development of
dissolved gases. O2 and CO2 are the main dissolved gases in
rechargeable SWBs and highlight the main practical issues
seawater. These gases for seawater are provided by the atmo-
ahead. We hope that this review will motivate and attract
sphere. However, the dissolved gas concentration depends on
many readers, graduate students, and young researchers to
the solubility and salinity, temperature, and pressure of
work in this new area and stimulate further research
seawater.40
progress.
2. Seawater 3. History: development of SWBs

Before discussing SWBs, we have to understand seawater and from primary (non-rechargeable) to
some of the properties that inuence SWBs' performance. secondary (rechargeable)
Water is the most abundant substance on Earth; nearly 71% of
the Earth's surface is covered by water. More importantly, of the Fig. 1 shows a diagram of the development history of SWBs from
total available water, 97.5% is seawater, while the remainder is a primary to a secondary system and their applications. In the
freshwater (2.5%).28,29 Seawater exists in oceans. Naturally, this past few years, SWBs have been the subject of renewed interest.
seawater is saline compared with freshwater due to the exis- Since the 1940s, seawater has been directly employed as an
tence of salts in the form of dissolved ions (note: there are 35 electrolyte in batteries (or electrochemical power cells); such
grams of salt in 1 L of seawater). Table 1 shows the concentra- batteries were later represented as SWBs. Mg (anode)–silver
tion of the major dissolved ions in standard seawater, where chloride (AgCl; cathode) batteries were the rst developed
Na+ (10.7 g) and Cl (19.3 g) ions are the main dissolved ions, commercial primary SWBs (from 1943), and they were originally
comprising 90% of all dissolved ions in seawater. Therefore, we particularly produced for military use (1943–45) and later for
can infer that Na+ and Cl ions are the main reason for the high civilian applications (1945–52).41 For the same purpose, due to
saline nature of seawater. Many of these dissolved salt ions in the high cost of the silver cathode, Mg–cuprous chloride (CuCl;
seawater are supplied to seas/oceans by rivers. In brief, while cathode) batteries were produced in 1949.41 However, the high
owing as river water on soil, the rainwater breaks rocks and hygroscopic nature of CuCl and its poor chemical stability
brings salts and minerals in the form of dissolved ions into the impelled the further development of a primary SWB system
ocean. Volcanic eruptions also provide some dissolved ions, employing cheap and stable cathode materials, such as lead
mainly chlorine and sulphur dioxides, to the ocean.30 However, chloride (PbCl2),42 mercurous chloride (Hg2Cl2),43 cuprous
22804 | J. Mater. Chem. A, 2019, 7, 22803–22825 This journal is © The Royal Society of Chemistry 2019
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Fig. 1 Timeline of SWBs and their major developments from a primary to a secondary system.
iodide (CuI),44 and cuprous oxide (Cu2O).45 Since these classical With the above primary SWBs, it is impractical to store
batteries are primary systems, they cannot be recharged aer electrical energy. Thus, in 2014, rechargeable SWB tech-
the rst discharge. Hereaer, it must be noted that classical nology was proposed and patented by Y. Kim's research
SWBs are denoted as primary SWBs. group; it uses seawater as the Na+ ion cathode for electrical
In the meantime, for deep-sea applications or long-term energy storage. This rechargeable SWB has a promising
underwater operation, metal (anode)–seawater (cathode) future in a broad range of applications such as ESSs for tidal
batteries, including the Mg–seawater battery46 and Al–seawater and wind power near coastal areas, an energy provider in the
battery,47 were developed as high-energy-density batteries military, and other civilian applications. The main aim of this
during the 1990s, and their long-term operation in the deep sea review article is to increase the prominence of rechargeable
was proven. These metal–seawater batteries can be operated via SWBs. In the following section, we will discuss the chemistry
two modes: (i) oxygen-reduction reaction (O2 + 2H2O + 4e / and structure of SWBs and their research, performance
4OH)47 on a cathode current collector with water (H2O) mole- metrics, and so on.
cules through the utilization of dissolved oxygen (O2) (DO) as
a cathode oxidant in seawater and (ii) hydrogen evolution (2H2O
+ 2e / H2 + 2OH)47 through the consumption of water 4. Rechargeable SWB structure and
molecules as a cathode oxidant supplied by seawater. This kind chemistry
of SWB also works on the principle of the primary concept.
Along with Mg, Al,48–51 and its alloys, Zn50 was also examined as Generally, as shown in Fig. 2a, the proposed rechargeable SWB
an anode in primary SWB systems. However, these tested metal consists of an anode in a non-aqueous electrolyte, seawater with
anodes showed a high self-discharge rate and their performance a cathode current collector, and a solid electrolyte (ceramic
was disturbed by electrode blockage owing to unwanted metal membrane) situated between the two electrodes and separating
hydroxide formation (MA + nOH / MA(OH)2 + ne; where MA the non-aqueous (liquid) electrolyte and seawater.26,57 The
means metal anode).35,52,53 Furthermore, the operating voltage rechargeable SWB has a cathode open-structured system;
of such batteries is very low (1 to 1.8 V) when using Mg, Mg usually, seawater is exposed to ambient air.58 The anode stores
alloys, Al, and Zn as the anode.54 As we know, the cell voltage is Na+ ions harvested from seawater by charging, so the anode
also one of the main dominating factors for the energy density plays a vital role in determining the rechargeable SWB energy.
of batteries. Therefore, in early 2006, the PolyPlus Battery The ceramic solid electrolyte plays a role as an electrolyte and
Company designed a primary-type Li–SWB to improve cell separator. Due to the excellent selectivity of the solid electrolyte,
voltage by using a protected lithium electrode as the anode. only Na+ ions are transported to the anode during the charging
This technological Li–seawater battery with DO enabled an process and they return from the anode to seawater during
experimental cell voltage of 3 V (vs. Li/Li+), and with hydrogen discharge. Other cations in seawater are blocked. Seawater is
evolution, this enabled an experimental cell voltage of 2.3 V (vs. a supplier of Na+ ions for anodic reactions during charging, and
Li/Li+).55,56 DO is an oxidant during discharging, so seawater acts as the
sole active cathode material.25 The current collector offers
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Fig. 2 (a) Schematic representation of the structure of rechargeable SWBs and their electrochemical process at the anode and cathode-side
during the charge and discharge process. (b) Simulated Pourbaix diagram for seawater at 25 C, where the chlorine system is constructed by
assuming a total chlorine concentration (CT.Cl) of 0.54 m, with chloride ions (Cl) as the only chlorine species, since a typical concentration of Cl
in seawater is z0.54 M. A H2O/O2 system is built by considering an O2 partial pressure (PO2) of 0.206 atm and activity coefficients for all species
are assumed to be 1. (c) Typical charge–discharge voltage profile of a rechargeable SWB using HC as the anode (HC|seawater). (b and c)
Reproduced with permission.25 Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
reaction sites for cathodic reactions and serves as the holder of at pH 8. Hence, the OER is the most probable reaction on the
the catalyst or active materials and paths for electrons.59,60 cathode current collector of the rechargeable SWB during the
The electrical energy in the rechargeable SWB is stored at the charging process. In case, the charging process for the SWB
anode side as Na metal by harvesting Na+ ions from seawater via appears over 3.95 V (vs. Na/Na+), that could belong to the HCFR
the oxygen evolution reaction (OER; reaction (1)) during the (eqn (2)) process.25
charging process. During the discharge process, easily reducible During discharge, suppose the ORR occurs by a two-electron
species of DO, which is present in seawater, are involved in the reduction pathway (O2 + H2O + 2e / HO2 + OH; E ¼ 0.21 V
oxygen reduction reaction (ORR; reaction (1)) with the aid of vs. SHE (at pH ¼ 8)), in contrast to a four-electron reduction
water while the stored chemical energy is released as electricity pathway (O2 + 2H2O + 4e / 4OH; E ¼ 0.77 V vs. SHE (at pH ¼
with Na+ ions transferred back from the anode into seawater 8)), the resultant theoretical cell voltage for this SWB will be
(reaction (2)). The half-cell (anodic and cathodic) reactions are 2.9 V (vs. Na/Na+). Anyway, this two-electron reduction pathway
stated below:25 process can be avoided by using the selective four-electron
Cathode (in seawater at pH ¼ 8): reduction pathway electrocatalysts. On the other hand, it must
be noted that when seawater does not have enough DO or using
4OH 4 O2 + 2H2O + 4e (ORR 4 OER), high current, the discharge process of the rechargeable SWB
E ¼ 0.77 V vs. SHE (1) can occur through the hydrogen (H2) evolution reaction (2H2O +
2e / H2 + 2OH; E ¼ 0.47 V vs. SHE (at pH ¼ 8)), and the
Anode (in a nonaqueous electrolyte): theoretical cell voltage will be 2.2 V (vs. Na/Na+).25 So, during
discharge, it is essential to maintain the concentration of DO in
4Na+ + 4e 4 4Na, E ¼ 2.71 V vs. SHE (2)
seawater and the use of optimized low current, which is more
The overall cell reaction in the rechargeable SWB during favorable for the ORR. Fig. 2c displays the typical charge and
charge/discharge is expressed below: discharge curves of a rechargeable SWB operated using hard
Overall reaction: carbon (HC) as the anode, respectively. The resultant charge
and its reversible discharge proles imply the sodiation and
4Na + O2 + 2H2O 4 4NaOH, Ecell ¼ 3.48 vs. Na/Na+ (3) desodiation processes through the OER and ORR processes,
respectively. The required Na+ ions for sodiation in HC are
Therefore, the theoretical cell voltage of the rechargeable harvested from seawater. However, it must be noted that the cell
SWB is approximately 3.48 V (vs. Na/Na+) (eqn (3)). voltage depends on the potential of the anode and kinetics of
As we know, the pH of standard seawater is approximately 8, the ORR process, and the voltage gap between the charge and
so during the charging process of the SWB at this pH, according discharge curves depends on the kinetics of both the OER and
to the Pourbaix diagram (Fig. 2b), a hypochlorite (ClO) ORR processes (which will be discussed in the following
formation reaction (HCFR; Cl + OH 4 ClO + H2O + 2e; E ¼ sections).
1.24 V vs. SHE)61 can also occur on the cathode current collector
in addition to the OER (eqn (1)). Here, the HCFR has a kinetic
advantage compared with the OER because the HCFR is a two-
5. Research progress on rechargeable
electron oxidation reaction and the OER process is based on SWBs
a four-electron oxidation reaction. However, as shown in the
Some primary SWBs, such as Mg–AgCl, Mg–CuCl, and Al–AgCl
Pourbaix diagram, the OER (0.77 V vs. SHE) is highly thermo-
batteries, have already been established efficiently and applied
dynamically favored over the HCFR (1.24 V vs. SHE) in seawater
mainly in military- and navy-related areas. However,
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rechargeable SWBs are still in the early R&D stage and needs use natural seawater in an open-structured cathode; the
a solution for various issues before their commercialization cathode part must be in direct contact with seawater, but the
(these will be discussed in the following sections). Therefore, for anode part should be completely sealed to avoid contact with
the practical application of rechargeable SWBs, structural seawater. Therefore, the tester design is also essential for
design, engineering, and optimal materials are still required obtaining consistent electrochemical performance. The
(i.e. the anode, nonaqueous electrolytes, cathode current assembled SWB coin-cell combines with the carbon-based
collector, and electrocatalysts). Fig. 3 shows the record of cathode current collector and can be loaded in the bolts/nuts-
research efforts, which have been moving toward the develop- type tester (Fig. 4a). The rst prototype, the bolts/nuts-type
ment of rechargeable SWBs for real-time applications. Each type tester, experienced the problem of seawater leakage between
of research progress is described in the following sections. the bolts and nuts (Fig. 4a). To solve this problem through the
engineering process, we developed a screw-type tester (Fig. 4b),
and, eventually, a ow-cell tester was also developed over the
5.1. Cell design and engineering: from proof-of-concept to past few years (Fig. 4c). Since rechargeable SWBs utilize
coin cells seawater as a cathode material, it is crucial to provide fresh
As shown in Fig. 2a, the rechargeable SWB system employs seawater to supply unlimited Na+ ions and oxygen (O2) to the
multilayer electrolytes consisting of a non-aqueous electrolyte, reaction sites continuously. For this reason, the ow-cell was
a solid electrolyte, and an aqueous natural seawater catholyte. designed, and the seawater and oxygen could circulate contin-
Due to these structural features, a new cell platform and testing uously (Fig. 4c).
environments are essential for testing rechargeable SWB To investigate the seawater ow effect, seawater cells were
systems. Initially, we hand-made a cell for the proof-of-concept tested using heat-treated carbon felt (HCF) as the cathode
of the rechargeable SWB26 by considering critical cell compo- current collector in the ow ON and ow OFF modes.58 Fig. 4d
nents. Although it conrmed the possibility of the development shows the charge/discharge voltage proles in the ow ON and
of rechargeable SWBs, due to the liquid leakage problem, it was ow OFF modes at a current rate of 0.025 mA cm2 for 5 hours.
changed to a pouch-type rechargeable SWB design.60,62 None- In the ow OFF mode, a large voltage gap (1.1 V) was observed
theless, the size of each cell is different for each researcher. and the terminal charge/discharge voltages were 3.9 V and
Hence, the results are different and so it is quite hard to acquire 2.8 V, respectively. On the other hand, in the ow ON mode,
consistent data for analysis. Therefore, it is imperative to the cell showed fast saturation of the charge/discharge voltage;
construct a standard cell platform and its testing conditions the charge/discharge terminal voltages were 3.7 V and 3.0 V,
considering the core components of rechargeable SWBs to respectively (DV ¼ 0.7 V). It should be noted that the seawater
obtain reliable and uniform data.25 Furthermore, we have ow effect plays an essential role in enhancing the voltage
developed a coin-type unit-cell (SWB2464) and prototype tester efficiency of rechargeable SWBs. To check the DO content in
of the rechargeable SWB (Fig. 4a and b).58 Rechargeable SWBs seawater, we examined the ow ON and ow OFF modes in the
Fig. 3 Various types of research progress involving developing high-performance rechargeable SWBs for commercial products for real-time
applications. The SEM image shown for electrocatalysts was adopted with permission.57 Copyright 2017, Royal Society of Chemistry. The images
shown for applications were adopted with permission.25 Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Fig. 4 (a) Prototype of a bolts and nuts type tester and (b) screw-type tester, where both types of testers are immersed in seawater for the
electrochemical test. (c) Assembled coin-type cell and optimised flow-type tester. (d) Charge/discharge voltage profiles of the cell measured at
a current rate of 0.025 mA cm2 for 5 h in the seawater flow ON and OFF modes (Na|seawater). (e) Discharge voltage profile of the cell measured
at a current rate of 0.1 mA cm2 and the dissolved oxygen (DO) content in seawater catholyte in the flow ON and OFF modes. (c–e) Adopted with
permission.58 Copyright 2017, Elsevier.
discharging process at a current rate of 0.1 mA cm2 (Fig. 4e). It nonaqueous electrolyte and seawater physically. There are three
can be seen in Fig. 4e that the DO content and the discharging kinds of solid electrolytes with the ability to conduct Na+ ions:
voltage were maintained at a certain level in the ow ON mode, inorganic, polymer, and polymer–ceramic composite.63–66
but the DO content and discharging voltage sharply decreased Among them, inorganic electrolyte has high density and high
to 5.9 mg L1 and 1.9 V, respectively, in the ow OFF mode. mechanical strength to separate the nonaqueous electrolyte and
As described above, the discharge process of the SWB is based seawater physically compared with polymer-based electrolytes
on the ORR, which consumes DO, showing that a sufficient because polymer-based solid electrolytes generally have weak
oxygen supply has an important inuence on the performance mechanical strength and relatively low density, which results in
of rechargeable SWBs. From these results, we conrmed that it physical cell failure and/or chemical cell failure (a mixture of
is important to supply adequate reactants (seawater and oxygen) organic liquid electrolyte and seawater). However, all inorganic
to the reaction sites (the surface of the cathode current solid electrolytes still cannot be used for rechargeable SWB
collector) through the seawater ow mode, and, consequently, application.
the overpotential arising from the OER/ORR can be reduced. The most well-known inorganic solid electrolytes are sulde
Based on these efforts, the potential of the SWB can be easily and oxide-based solid electrolytes (Fig. 5b and c). The sulde-
tested, and its results can be compared with those collected by based solid electrolyte is a promising solid electrolyte for
other research groups. sodium batteries due to its ductile mechanical properties and
high ionic conductivity (>1 103 S cm1 at room temperature
5.2. Selective Na-ion-conducting solid electrolytes (RT)) derived from the large ionic radius of sulfur and weaker
(membranes) electrostatic interaction with Na+ ions. However, these sulde-
based solid electrolytes are unstable in humidity and air.
The selective Na-ion-conducting solid electrolyte is at the heart
Na3PS4 and Na3SbS4 are examples of sulde-based solid elec-
of constructing and demonstrating the rechargeable SWB
trolytes.63,64,67,68 Na3PS4 can quickly react with water and oxygen,
concept, as shown in Fig. 2a. The solid electrolyte used in the
producing toxic H2S gas, while Na3SbS4 also with water forms
SWB should have the features (Fig. 5a) of high (Na+) ionic
the Na3SbS4$xH2O phase, resulting in low ionic conduc-
conductivity at a low temperature, high ionic (Na+) selectivity (it
tivity.69–71 In contrast, oxide solid electrolytes are impermeable,
should not allow any ions other than Na+), electrical insulation
white ceramics that have higher chemical stability and signi-
properties to separate the anode and cathode, high chemical
cant mechanical strength with high ionic conductivity. The
stability against seawater and nonaqueous electrolytes, elec-
representative examples of oxide solid electrolytes are b-
trochemical stability while operating in a wide electrochemical
alumina and NASICON (Na super ion conductor;
window, and high mechanical/physical strength to separate the
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Fig. 5 (a) Requirements of solid electrolytes for rechargeable SWBs. (b) Representative sulfide solid electrolytes and their general properties. (c)
Representative oxide solid electrolytes and their general properties. (a) Adopted with permission.67 Copyright 2018. Cell Press. (b) Na3PS4 and
Na3SbS4 structures adopted with permission.68 Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Na–b00 -alumina structure
adopted with permission.74 Copyright 2017, Elsevier. (c) NASICON structure reproduced with permission.66 Copyright 2018, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.
Na1+xZr2SixP3xO12).63,64 More information regarding beta- by Hong and Goodenough in 1976.77,78 The general formula of
alumina and NASICON can be obtained from the following NASICON is Na1+xZr2SixP3xO12, where 0 # x # 3,79 which
subsections. results from NaZr2P3O12 solid solution with the partial
5.2.1. b-alumina solid (ceramic) electrolyte. The b-alumina replacement of P by Si. The nominal composition for achieving
electrolyte, produced from oxides and hydroxides of aluminum, better conductivity is Na3Zr2Si2PO12 (at x ¼ 2). NASICON
sodium, and lithium, was discovered in 1967,72 and has two generally forms in two phases (crystal structure), which are
crystal structures,73,74 i.e., sodium–b-alumina (Na–b-Al2O3) and
sodium–b00 -alumina (Na–b00 -Al2O3) (see Fig. 6a). Both have
a layered crystal structure and sodium ions transferred through
a two-dimensional (2D) sodium conduction plane. However,
they have different compositions and crystal structures. Na–b-
Al2O3 is Na2O$xAl2O3 (x ¼ 8–11) with a hexagonal structure. On
the other hand, Na–b00 -Al2O3 is Na2O$xAl2O3 (x ¼ 5–7) with
a rhombohedral structure. The higher sodium content in the
conduction plane of Na–b00 -Al2O3 yields higher ionic conduc-
tivity (2 103 S cm1 at room temperature)75 than b-
alumina. Therefore, Na–b00 -Al2O3 was a successfully adopted
solid electrolyte in electrochemical ESSs, particularly in
sodium–sulfur (Na–S) batteries and sodium–metal chloride or
ZEBRA (zero emission batteries research activity) batteries,73
where it separates the cathode and anode and acts as a fast Na-
ion-conducting solid electrolyte. In this sense, we have used
commercially available Na–b00 -Al2O3 to construct an SWB;
however, this electrolyte is sensitive to water induced by the
slow diffusion of H3O+ ions into the Na–b00 -Al2O3 phase.
Therefore, an SWB with an Na–b00 -Al2O3 solid electrolyte and
a poor cycle life (Fig. 6b) was observed with AlOOH phase
formation. AlOOH formation was conrmed by comparing the
XRD result of the Na–b00 -Al2O3 solid electrolyte before and aer
Fig. 6 (a) Schematic diagram of Na–b-alumina and Na–b00 -alumina
cycling, as shown in Fig. 6c. With the AlOOH phase, the ionic structures. (b) Charge–discharge curve of a rechargeable SWB (hard
conductivity of this electrolyte was dramatically decreased, carbon/Na–b00 -alumina/seawater). (c) XRD patterns of Na–b00 -alumina
inducing signicant overpotential.76 before and after cycling in the rechargeable SWB (HC|Na–b00 -alumi-
5.2.2. NASICON solid (ceramic) electrolyte. The term na|seawater); A indicates the formed AlOOH phase after 10 cycles. (a)
Reproduced with permission. Copyright 2017, Elsevier.74 (b and c)
NASICON (sodium (NA) SuperIonic CONductor) was proposed
Adopted with permission. Copyright 2017, Elsevier.76
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rhombohedral and monoclinic (see in Fig. 7a),66 and it is worth with seawater since it is exposed to seawater directly. In
noting that this different phase formation depends on its previous studies, NASICON was found to be unstable with
composition and synthesis temperature.80 However, both pha- water. However, the testing conditions of the studies were
ses comprise three-dimensionally (3D) linked ZrO6 octahedra different from those of the rechargeable SWB, such as deion-
sharing corners with SiO4 and PO4 tetrahedra and offer a 3D ized (D.I.) water and high temperature. To evaluate recharge-
pathway for Na+ transportation. able SWB applicability, a NASICON pellet was exposed to
The procedures for NASICON synthesis are more convenient seawater for about two months and it was conrmed through
than those for b-alumina synthesis. So far, various synthesis SEM and XRD analysis (not shown here) that there was no
methods (e.g., sol–gel, spark-plasma sintering, solid-state reac- signicant surface degradation or phase changes,25 respec-
tion, combustion, ion exchange, and hydrothermal reaction) tively. Moreover, in the preliminary studies, the rechargeable
have been used to fabricate NASICON; however, some only SWB built with NASICON showed a stable cycle performance
contribute to achieving a highly dense NASICON with the ex- over 200 cycles, while NASICON retained its phase stability
pected conductivity. Since 2014, Y. Kim's group has been (Fig. 7f).76 Later, we successfully cycled the rechargeable SWB
involved in the fabrication of NASICON pellets via the solid- for 600 cycles81 as shown in Fig. 7g, which further conrms the
state reaction route, as mentioned in the steps in Fig. 7b. potential of NASICON and its real-time applicability in
Now, two different NASICON shapes (viz. a circle and square, as rechargeable SWBs. Furthermore, it was more stable against
shown in Fig. 7c and d) are commercially produced from a non-aqueous electrolyte (1 M NaCF3SO3 in TEGDME (tetra-
4TOONE Co. Ltd (http://www.4toone.com). The bulk density ethylene glycol dimethyl ether)) and a Na metal anode at the
and ionic conductivity of this commercially available NASICON anode side of the rechargeable SWB cell.23 Therefore, NASI-
are >3.03 g cm3 (>93% of theoretical density value) and 1 CON is still the most appropriate solid electrolyte in
103 S cm1, respectively.25 Fig. 7e shows the backscattered rechargeable SWBs.
electron image of a square shape NASICON pellet. There are 3
phases that exist in a NASICON pellet, i.e. NASICON,
5.3. Cathode compartment
amorphous and ZrO2, where NASICON grains are attached to
each other and the supports to transferred Na ions through As shown in Fig. 2a, the cathode compartment of the
the NASICON grains and their grain boundary. rechargeable SWB consists of a cathode current collector and
With the feature of 3D Na+ pathway conductivity, various seawater. The operation of the rechargeable SWB depends on
NASICON applications have been recognized, such as ZEBRA the sluggish OER/ORR process; thus, the electrocatalyst was
batteries, CO2 sensors, and sodium batteries; therefore, we also used on the current collector as a critical component to
expect it to be a good candidate for building an SWB. However, enhance the reaction kinetics. Additionally, each component in
for rechargeable SWB applications, NASICON should be stable the cathode part played a distinctive role. In the subsequent
subsections, we have described the research progress of these
Fig. 7 (a) Schematic illustration of the rhombohedral and monoclinic structures of NASICON, where, in the monoclinic structure, three Na+
interstitial sites (Na1, Na2 and Na3) are located between polyhedrons, featuring two Na+ transfer channels (Na1–Na2 and Na1–Na3) and in the
rhombohedral structure, two Na+ interstitial sites (Na1 and Na2) are located between polyhedrons, which offer only one Na+ transfer channel
(Na1–Na2). (b) Solid-state reaction route of NASICON. (c) Square and (d) circle type NASICON pellets that are available commercially. (e) The
backscattered electron image of a square shape NASICON pellet. (f) XRD patterns of the surface of the NASICON pellet before and after 100
cycles in a rechargeable SWB (HC|NASICON|seawater). (g) Charge–discharge curve of the rechargeable SWB (HC|NASICON|seawater). (a)
Reproduced with permission.66 Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (f) Adopted with permission.76 Copyright 2017,
Elsevier. (g) Adopted with permission.81 Copyright 2017, Elsevier.
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cathode components and their inuences on the performance improve the OER and ORR activity. An electrocatalyst is a cata-
of rechargeable SWBs. lyst that enhances electrochemical reactions and can modify
5.3.1. Current collector. The cathode current collector and increase the rate of chemical reactions without being
plays an essential role in determining the performance of consumed in the process. Generally, the available commercial
a rechargeable SWB as it provides reaction sites for the cathode electrocatalysts are mostly noble metal-based, such as Pt, Ru,
reactions (OER/ORR) as given in eqn (1) and electron paths. and Ir. The IrO2- and RuO2-based electrocatalysts are consid-
Hence, the cathode current collector for a rechargeable SWB ered the best electrocatalysts for the OER87 and Pt/C for the
should be selected based on the criteria of high electronic ORR,88 therefore making them inadequate for use as bifunc-
conductivity, large surface area, strong electrochemical and tional catalysts in a rechargeable SWB. The high cost and
mechanical stability, uniformly distributed transport area, cost- scarcity of noble metals also hinder their widespread use in
efficiency, lightness of weight, and wide availability for large-scale applications.89 For efficient bifunctional (OER/ORR)
commercial purposes. Metal (or its alloy) and carbon-based electrocatalytic activity, the electrocatalyst should possess the
collectors are the most-used current collectors in various following features: (i) high active site density and uniform
kinds of battery systems. However, it must be noted that distribution for low OER and high ORR onset potential and high
employing current collectors varies from system to system catalytic activity, (ii) a large surface area and a sufficiently
based on electrochemical potentials and electrolyte mediums. porous structure for sufficient mass transfer pathways and
According to previous reports, except for titanium and its alloys, enhanced electrode kinetics, (iii) a robust architecture for
other metal-based materials cannot be used in the medium of chemical and mechanical stability for high durability, (iv) high
seawater as a cathode current collector due to their instability mass and volumetric activity, and nally (v) an abundant
with seawater. The existence of chloride ions in seawater can resource with a low cost. Therefore, we prepared and tested
easily destroy the oxide lm on the surface of other metals and several bifunctional electrocatalysts in an SWB as substitutes to
form a complex with metal ions, resulting in the corrosion of noble metals. Based on reports found in the literature, bifunc-
metals in seawater.82,83 Nonetheless, Ti-based current collectors tional electrocatalysts can be classied into three groups: non-
are also not suitable for use in SWBs as they are not electro- precious metal-based catalysts, carbon-based catalysts, and
catalytically active in nature toward the OER/ORR reactions. hybrid catalysts. This section will provide the research efforts
On the other hand, carbon-based current collectors have that have been made on different electrocatalysts to obtain
been recognized for their high corrosion resistance in seawater enhanced performance in rechargeable SWBs.
and then utilized in primary SWB applications as cathode 5.3.2.1. Non-precious metal oxide-based electrocatalysts. Non-
current collectors for ORR and HER activity.84,85 Based on these precious metal oxide-based electrocatalysts are a great alterna-
characteristics, carbon paper was rst tested in a rechargeable tive to noble metal-based electrocatalysts because of their earth-
SWB in the search for a suitable cathode current collector.26 abundance, acceptable price and easy preparation compared
Unfortunately, due to its poor mechanical stability (easily with a noble metal catalyst, which makes them more suitable
broken), carbon felt86 was later used. Carbon felt features for practical application.90,91 Besides, some great approaches
mechanical stability and also offers high conductivity and have been proposed in recent studies to improve the catalytic
exibility. However, pristine carbon felt shows very poor activity of metal oxide-based electrocatalysts, including tuning
wettability against seawater due to the presence of a hydro- their elemental composition and creating porous nano-
phobic surface, which mainly emanates from the existence of structures to increase the density of active sites. Accordingly,
sizing agents in pristine carbon felt for mechanical reinforce- Abirami et al. prepared highly porous cobalt-manganese oxide
ment. Thus, before use in an SWB, pristine carbon felt was (CoxMn3xO4) nanoparticles (see the TEM image in Fig. 8a) with
subjected to heat treatment at 500 C for 2 or 3 h in ambient air a surface area of 64.5 m2 g1 by using Mn[Co(CN)6]2$nH2O as
to become hydrophilic.58 The contact angle results (not shown a precursor and employed them as a bifunctional electrocatalyst
here, refer ref. 58) showed a difference in the hydrophobic in SWBs.92 The SWB cell containing the CMO exhibited
nature of the pristine carbon felt, and the hydrophilic nature of a signicantly reduced voltage gap (DV 0.53 V) (Fig. 8b) with
heated carbon felt with seawater. The wettability of heated a voltage efficiency of 85% compared to that of the cells
carbon felt is a result of the introduction of hydrophilic surface containing Pt/C (0.64 V) or Ir/C (0.73 V), or without any
functional groups (i.e., C]O and C–O). Subsequently, the catalyst (1.05 V) at a current density of 0.01 mA cm2, as well
heated carbon felt relatively lowered the voltage gap (DV 1.4 V) as stable performance during 100 cycles. Shin et al. reported the
of the rechargeable SWB compared to pristine carbon felt (DV synthesis of cobalt vanadate (Co3V2O8) nanoparticles as an
1.6 V) (not shown here, refer ref. 58), which implies improved electrocatalyst for SWB application.93 The Co3V2O8 improved
OER/ORR activity of heated carbon felt. the kinetics of the OER/ORR and exhibited a small voltage
5.3.2. Electrocatalysts. The rechargeable SWB with the difference of 0.95 V at 0.1 mA cm2 during 20 cycles (total 400 h)
aforementioned carbon current collectors still shows a low with a voltage efficiency of 76%.
voltage efficiency with a large voltage gap (1.0 V) between 5.3.2.2. Carbon-based electrocatalysts. Carbon-based elec-
charge and discharge voltage curves due to the sluggish kinetics trocatalysts are also known as metal-free electrocatalysts and
of the OER and ORR processes. In these circumstances, to because of their large surface area, various structures, and cost-
diminish charge–discharge voltage gaps, it is desirable to effectiveness are considered as alternatives to expensive noble
employ electrocatalysts on the cathode current collector to metal-based catalysts. Therefore, carbon-based electrocatalysts
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Fig. 8 (a) TEM image of CoxMn3xO4. (b) Charge–discharge profile of a rechargeable SWB (Na|seawater) using CoxMn3xO4 derived from Mn
[Co(CN)6]2$nH2O as a precursor where its performance is compared with that of a cathode current collector (carbon paper) and different
electrocatalysts (i.e. Pt/C and Ir/C). (c) SEM image of porous carbon. (d) Charge–discharge profiles of a rechargeable SWB (Na|seawater) using
porous carbon derived from grapefruit peel where its performance is compared with that of a cathode current collector (carbon paper) and
various electrocatalysts. (e) TEM image of a S–rGO–CNT–Co catalyst. (f) Charge–discharge profiles of the rechargeable SWB cell using the S–
rGO–CNT–Co catalyst where its performance is compared with that of a cathode current collector (carbon paper) and Pt/C. (g) SEM image of
carbon sponge. (h) Charge–discharge profiles of the rechargeable SWB cell (Na|seawater) using 3D macroporous carbon sponge where its
performance is compared with that of cathode carbon felt, grind carbon sponge, Pt/C and IrO2. (a and b) Reproduced with permission.60
Copyright 2016, American Chemical Society. (c and d) Adopted with permission.57 Copyright 2017, Royal Society of Chemistry. (e and f)
Reproduced with permission.140 Copyright 2017, Elsevier. (g and h) Reproduced with permission.102 Copyright 2018, Elsevier.
are also one of the most examined electrocatalysts in metal–air polydopamine (PDA) nanospheres and studied their feasibility
battery systems which are operated based on the OER and in a rechargeable SWB. The rechargeable SWB tested with NSCS
ORR.94,95 The widely studied carbon-based electrocatalysts showed a low voltage gap (DV 0.56 V), round-trip efficiency
include porous carbon, graphene, carbon black, nanotubes, and (84%), and outstanding cycle stability up to 100 cycles.
nanobers that are usually doped with heteroatoms (S, N, O, P 5.3.2.3. Hybrid or composite electrocatalysts. Metal oxide-
and B) and/or contain defective carbon atoms.95–98 Therefore, to based catalysts show better bifunctional OER and ORR cata-
obtain a high performing OER and ORR, carbon catalysts lytic activity, but typically they face two main issues. One is poor
require a careful and creative choice of carbon sources, doping electrical conductivity, and another is fast degradation of active
sources, carbon precursor, template, and synthetic conditions. sites by particle aggregation during redox reactions, which
Based on the above context, we fabricated porous carbon should be rectied for their practical use.91,94 Therefore, to solve
catalysts with high surface areas, defects, and self-doped oxygen these issues, metal-based catalysts are mixed with carbon
functional groups which were prepared from an organic bio- materials to make a composite. One-dimensional carbon
waste of grapefruit peel using hydrothermal carbonization nanotubes (CNTs) with the encapsulation of cobalt-based
combined with the chemical activation process.99 The nanoparticles on a three-dimensional internetworked reduced
rechargeable SWB with this porous carbon (see the SEM image graphene oxide (named as S–rGO–CNT–Co) were synthesized
in Fig. 8c) catalyst exhibited excellent cycling stability with (see the TEM image in Fig. 8e) by using steam activation and
a narrow voltage gap (DV 0.47 V) during 100 cycles compared microwave irradiation.59 The as-prepared material was used as
to other electrocatalysts, such as Pt/C (0.68 V), IrO2 (0.66 V), a bifunctional electrocatalyst in the cathode current collector of
MnO2 (0.73 V), and Vulcan X72 (0.80 V) (Fig. 8d). This an SWB cell. The cell showed a small voltage gap (DV 0.42 V)
grapefruit derived porous carbon can be an excellent/cost- compared to bare carbon paper (0.88 V) at a current density of
efficient substitute for the expensive carbon materials of gra- 0.01 mA cm2 (Fig. 8f).
phene and carbon nanotubes. Jeoung et al.86 prepared porous N- 5.3.2.4. Current collector cum electrocatalyst. All the above
doped carbon (PNC) by using thermolysis of a Zn-based metal– electrocatalysts were mostly prepared or used in the form of
organic framework [Zn(FMA)(4-(phenylazo)pyridine)2(H2O)] in powder. Thus, to attach them on cathode current collectors of
an inert atmosphere. The PNCs demonstrated in the recharge- rechargeable SWBs, it is necessary to use inactive binders.
able SWB featured low voltage gaps of <0.53 V at 0.01 mA cm2. However, binders are usually a form of insulating polymer and
Similarly, Khan and his co-researchers100 synthesized N-doped thus can hinder the ion and electron transport in the system,
and N, S-doped carbon nanosphere (referred to as NCS and resulting in an inuence on the overall performance of elec-
NSCS, respectively) electrocatalysts by using pyrolysis of trocatalysts, and also increase the production costs of the
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battery.101 Therefore, Zhang and his co-researchers in our group Ag/AgCl reaction delivers an enhanced electrochemical perfor-
prepared 3D macroporous carbon sponges (see the SEM image mance compared to the OER/ORR processes that occur on
in Fig. 8g) and directly employed the sponges as a cathode carbon felt (i.e. common cathode reaction in the rechargeable
current collector as well as a carbon-based electrocatalyst for the SWBs). The obtained voltage gap and voltage efficiency for the
OER/ORR in a rechargeable SWB.102 Interestingly, the tested Ag electrode are 0.3 V and 90.3%, while they are 1.58 V and 73%
SWB using a carbon sponge exhibited a small charge–discharge for carbon felt (Fig. 9b). However, Ag is very expensive and not
voltage gap (DV 0.46 V) and high voltage efficiency (83.2%) a practical/viable cathode for real-time application. Recently, Bi
with long term cycling stability (100 cycles) (Fig. 8h). (bismuth),106 BiOCl (oxychlorides),107 polypyrrole,108 and poly-
5.3.3. SWB with non-OER/ORR cathode chemistry. Even silsesquioxane109 have also been considered as potential chlo-
aer using an electrocatalyst on a cathode current collector, the ride storage materials; thus we hope that they could be our
voltage gap is still high due to the slow kinetic nature of the OER future alternative cathode for the expensive Ag.
and ORR processes. Therefore, to achieve a smaller voltage gap, On the other hand, nickel hexacyanoferrate (NiHCF) with
SWBs with other cathode chemistries (see Fig. 9a) such as (i) intercalation/deintercalation characteristics was used as the
chloride (Cl) capture/release reaction, (ii) intercalation/ cathode. The assembled SWB with NiHCF103 showed a relatively
deintercalation, and (iii) a combined intercalation/ small voltage gap between the charge–discharge curves with
deintercalation and OER/ORR process have also been reported a typical discharge voltage of 3.4 V (Fig. 9c), owing to the highly
elsewhere.103–105 It is worth noting that the SWB was operated reversible and fast Na-ion intercalation/deintercalation charac-
based on intercalation/deintercalation and chloride (Cl) teristics of NiCHF. However, in the above strategies, the voltage
capture/release reactions where seawater acted as an electrolyte. efficiency can be improved, but the energy is limited by the
Nonetheless, for intercalation/deintercalation combined with amount of cathode chemistry. Recently, to enhance the energy
the OER/ORR processes, seawater acted as both an electrolyte performance, Na0.5Co0.5Mn0.5O2 (NCMO, P2-type layered oxide)
and a cathode. was employed105 as the cathode for Na-ion intercalation/
As we know, seawater contains more than enough Cl ions. deintercalation and as the electrocatalyst for the OER and
Therefore, when using Ag as a cathode in an SWB,104 the ORR processes. As we expected, NCMO showed a dual electro-
reversible redox reaction of Ag/AgCl (Ag (s) + Cl (aq) 4 AgCl (s) chemical process, i.e. intercalation/deintercalation and OER/
at 2.9 V vs. Na+/Na) can occur during the cell operation. This ORR during the charge and discharge operations, as shown in
Fig. 9 (a) Other cathode chemistries apart from the OER/ORR used for rechargeable SWBs. (b) Charge and discharge profiles of a rechargeable
SWB using Ag as a cathode for chloride (Cl) capture/release reaction and a comparison of its performance with that of a carbonaceous
electrode. (c) First ten charge–discharge curves of a rechargeable SWB using a NiHCF cathode for Na-ion intercalation/deintercalation. (d)
Charge–discharge profiles of NMCO and a comparison of its performance with that of carbon felt. NMCO offers Na ion intercalation/dein-
tercalation and OER/ORR processes. (b) Adopted with permission.104 Copyright 2016, Elsevier. (c) Adopted with permission.103 Copyright 2017,
Elsevier. (d) Reproduced with permission.105 Copyright 2018, Royal Society of Chemistry.
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Fig. 9d, where the OER occurs followed by Na+ intercalation and
ORR occurs followed by Na+ intercalation. This dual electro-
chemical process characteristic of NCMO was further conrmed
via cyclic voltammetry analysis by the authors.105 Because of
NCMO, a reasonably reduced voltage gap (0.78 V) was attained
for the assembled SWB (Na/seawater/NCMO@carbon felt). This
obtained smaller voltage gap was much better than that of the
carbon felt (1.06 V) and closer to that of Pt/C coated carbon felt
which was used only for the OER/ORR processes. Anyway,
NiHCF and NCMO are not the only limited materials for Na-ion
intercalation/deintercalation and dual electrochemical process
(intercalation/deintercalation and OER/ORR); however, still

many materials are available that could also be studied at the
cathode side of this SWB. Na2Ni0.4Co0.6[Fe(CN)6]
(85 mA h g1),110 FeFe(CN)6 (125 mA h g1)111 and Na2Mn
[Mn(CN)6] (209 mA h g1)112 can be considered for the Na-ion
Fig. 10 Average redox potential versus gravimetric capacity of various
intercalation/deintercalation process with high capacity. anode materials which can be used for Na ion storage in rechargeable
Na0.95MnO2 (42 mA h g1),113 NaMn9O18 (45 mA h g1),114 SWBs.
Na0.44Mn0.44Ti0.56O2 (76 mA h g1)115 and NaNi0.33Mn0.33-
Co0.33O2 (120 mA h g1)116 can be used for a dual electro-
chemical process or only for the Na-ion intercalation/ can encourage the achievement of a high cell voltage (3.48 V
deintercalation process. vs. Na/Na+) in rechargeable SWBs (see eqn (1)–(3)) and then this
achieved high cell voltage along with the high capacity could
furnish high energy density rechargeable SWBs (theoretically
5.4. Anode compartment
4057 W h kg1 with respect to the Na anode). Taking full
The anode compartment comprises an anode and nonaqueous advantage of Na, we used Na as an anode in rechargeable SWBs
electrolyte. Both play a critical role together in the SWB. The in two different forms, individually, i.e. (i) Na harvested from
anode has more responsibility for electrical energy storage by seawater by charging124 and (ii) Na metal (commercially avail-
harvesting Na-ion from seawater, which can readily supply an able).26 However, because of the highly reactive nature of Na,
unlimited number of Na ions while owing through the during the charging process, electrodeposited Na shows
rechargeable SWB. The non-aqueous electrolyte acts as an ionic a tendency towards dendrite formation and growth. Also, Na
transport medium between the anode and a solid electrolyte anodes typically suffer from unstable solid-electrolyte inter-
during the charging and discharging processes and it is phase (SEI) layers and large electrode dimensional changes
generally also one of the main factors that inuence the cycling upon repeated plating/stripping. Consequently, rechargeable
performance by offering interfacial stability to the anode and SWBs face several problems: low cycling, low rate capability,
voltage window stability. We have described in the subsequent and low coulombic efficiency.124,125
subsections the research studies that have been carried out so To enhance the lifespan of Na anodes, there are several
far on the anode and non-aqueous electrolyte to develop approaches that have been developed126 to prevent dendrite
rechargeable SWBs. growth and form a uniform and stable SEI layer on Na anodes
5.4.1. Anodes. The anode materials that are reported or by using articial SEI layers on Na metal, additives in the elec-
considered for a sodium-ion battery can be used as an anode in trolyte, electrolytes with super concentrations, three dimen-
rechargeable SWBs as well. There are several kinds of feasible sional (3D) current collectors, Na/carbon anodes, and nanoscale
anode materials available for sodium storage: sodium metal interfacial engineering. With this background, to build anode-
(Na) or harvested sodium from the seawater cathode, interca- free rechargeable SWBs, graphene-coated Cu (graphene/Cu)
lation materials (hard carbon (HC), TiO2, Na2Ti3O7, etc.), alloy- current collectors have been developed using a chemical
ing materials (Bi, Sn, SnSb, P, etc.), conversion materials (Fe2O3, vapour deposition method by D. H. Kim et al.127 Before their use
MoS2, NiO, etc.), conversion-alloying materials (Sb2S3, SnS2, etc.) in rechargeable SWBs, the graphene/Cu current collectors are
and organic materials (Na2C8H4O4) (see Fig. 10).22,117–120 The subjected to a galvanostatic plating and stripping test using
search for appropriate anodes for rechargeable SWBs is not an a symmetric (graphene/Cu|separator|Na anode) cell architec-
easy task; however, some of the materials have been reported to ture. Graphene/Cu current collectors compared to Cu current
be useful as anodes in rechargeable SWBs, such as hard collectors lower the nucleation overpotential (40 mV), stabilize
carbon,99 antimony sulde (Sb2S3),121 tin/carbon (Sn/C),122 and plating/stripping (Fig. 11a), and stabilize coulombic efficiency
phosphorus/carbon (P/C).123 even aer 200 plating/stripping cycles (not shown here; see ref.
5.4.1.1. Sodium metal. When considering its low electro- 127). When using this graphene/Cu current collector in
chemical potential and high capacity, sodium (ENa+/Na ¼ 2.71 V a rechargeable SWB, a stable voltage plateau is obtained with
vs. SHE and 1166 mA h g1)124 could be an ideal anode material a more extended cycling prole compared to a Cu current
for rechargeable SWBs. The low electrochemical potential of Na
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Fig. 11 Comparison of (a) cycling performance of graphene-covered Cu (red line) and pristine Cu (black line) current collectors at 0.32 mA cm2
for 1000 s in 1 M NaOTF/DME electrolyte. (b) Galvanostatic discharge–charge profiles of rechargeable SWB cells with graphene Cu (red line) and
pristine Cu (black line) current collectors at 0.075 mA cm2. SEM images of plated Na from seawater on (c) graphene covered Cu and (d) pristine
Cu metal current collectors (0.675 mA h cm2 (0.075 mA cm2) for 9 h). (e) Comparison of cycling performance of a Na/C composite anode
and bare Na anode at 3 mA cm2. SEM images of the (f) Na/C composite anode and (g) bare Na anode after cycling (scale bars ¼ 40 mm). (h)
Galvanostatic discharge–charge profiles of rechargeable SWB cells containing a Na/C composite anode and bare Na anode at different current
densities from 0.5 to 3 mA. (a–d) Reproduced with permission.127 Copyright 2018, Royal Society of Chemistry. (f–h) Reproduced with
permission.125 Copyright 2019, American Chemical Society.
collector (see Fig. 11b).127 From the SEM image, it was distin- hysteresis beyond 80 h in the asymmetric cell test at 3 mA cm2,
guished that the plated Na metal on graphene/Cu current but the bare Na anode showed unstable and uctuating
collectors of rechargeable SWBs have a large grain size, fewer hysteresis even aer 10 h under the same testing conditions (at
nuclei, and a smooth surface (Fig. 11c), unlike a Cu current 3 mA cm2) (Fig. 11e). The Na/C anode showed an almost
collector (Fig. 11d). Similarly, the feasibility of a Cu pre- smooth surface (Fig. 11f) and the bare Na anode showed porous
patterned Al current collector was examined by Jung et al. for and uneven surfaces (Fig. 11g). It is suggested that the stable
metal-free rechargeable SWBs.128 From the symmetric cell test, cycle performance for the Na/C anode came from its even and
it was found that Na prefers Cu surfaces for its deposition rather smooth surface. Consequently, the performance of the Na/C
than Al within the current collector, and Na islands later anode was checked in a rechargeable SWB. The high surface
merged to form a lm-like aggregation. Therefore, the authors area feature of the Na/C anode decreased the local current
anticipated that this lm-like aggregation could control the density and resulted in a lower voltage gap even at a high
dendrite growth in rechargeable SWBs. As expected, current compared to the bare anode (see Fig. 11h).125
a rechargeable SWB with a Cu pre-patterned Al current collector Anyway, the direct use of the Na anode in rechargeable SWBs
exhibited a signicant increase of coulombic efficiency which could create a re safety issue during operation, as it tends to
was maintained at approximately 98% over 200 cycles, which is react with water (seawater). To address this concern, it is
much better (four times) than a Cu collector rechargeable SWB. essential to use an alternative anode to Na metal with high cycle
On the other hand, Go et al.125 prepared Na/carbon stability, high reversibility, and low electrochemical potential.
composite anodes by immersing 3D carbon cloth in melted 5.4.1.2. Na intercalation hard carbon (HC). Among the
Na (melt infusion strategy) for use in rechargeable SWBs. The carbonaceous anode materials, HC can be a leading anode for
resulting anodes exhibited a stable potential and a small sodium storage in sodium-ion batteries due to their low average
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operating potentials and relatively high reversible specic Fig. 12c, a stable discharge capacity was noted. Besides, when
capacities. In the early 2000s, Stevens and Dahn rst studied its a porous cobalt-manganese oxide (CoxMn3xO4) was used on
Na storage ability. HC is also known to be non-graphitizable, the cathode current collector of an HC-based rechargeable
and its structure typically contains small turbostratic (few- SWB,92 the results showed an increased reversible discharge
layer-stacked graphite) nano-domains with nanovoids which capacity (190 mA h g1), high energy efficiency (74–79%),
exist in between these nano-domains. Hence, HC (commercial) and stable cycle performance over 100 cycles. These results were
was rst studied as a metal-free anode in a rechargeable SWB obtained under the capacity cut-off condition of 200 mA h g1
battery. In Fig. 12a, (i) and (ii) show the normalized charge and upon charging and a voltage cut-off condition of 0.5 V upon
discharge curves of a cathode half-cell (Na/seawater/carbon felt discharge (0.01 mA cm2).
(cathode current collector)) and an anode half-cell (Na/HC) and 5.4.1.3. Alloy-based materials (Sb2S3, Sn/C and P/C). HC
(iii) displays a comparison of the measured and simulated exhibits a consistent discharge capacity with relatively small
charge and discharge curves of metal-free (or full cell) volume expansions during the electrochemical insertion/
rechargeable SWBs (HC/seawater/carbon felt). More interest- extraction reaction with Na+ ions harvested from seawater
ingly, it can be seen that the simulated and measured charge cathodes. However, HC still suffers from limited capacity utili-
and discharge curves provide a similar result. Senthilkumar zation due to their intrinsic constraint ascribed to their struc-
et al.99 tested a HC-based metal-free rechargeable SWB with tures which can lower the specic energy density of
a combination of a grapefruit peel derived porous carbon elec- rechargeable SWB systems. As an alternative to HC, so far
trocatalyst under a capacity cut-off condition of 200 mA h g1 Sb2S3,121 Sn/C122 and P/C123 were investigated as potential high
upon charging, and a voltage cut-off condition of 0.5 V upon capacity anodes for Na-ion storage in SWBs because they can
discharge (0.05 mA cm2). Fig. 12b shows the improved store a large number of Na ions in the host structure with
performance of the HC-based rechargeable SWB aer using a relatively low operating potential (below 1.0 V).
a porous carbon electrocatalyst on a cathode current collector The advantages of Sb2S3 are its high theoretical capacity
(carbon paper). Notably, the HC-based rechargeable SWB (946 mA h g1) compared to Sb (660 mA h g1) for Na insertion,
exhibits a discharge capacity of 191 mA h g1 (at the 7th cycle), as well as an expected improvement in mechanical stability due
a voltage efficiency of 83–84% and an excellent life over 100 to smaller volume changes during charge and discharge from
cycles (Fig. 12c). In the cycling result, it can be noted that the the suldes. This high capacity feature comes from the
discharge capacity and coulombic efficiency were relatively low combination of a conversion reaction (Sb2S3 + 6Na+ + 6e /
during the initial cycling of approximately four cycles because of 2Sb + 3Na2S) and an alloying reaction (2Sb + 6Na+ + 6e /
the development of the solid electrolyte interface (SEI) layer on 2Na3Sb).129,130 For SWB's anode application, Hwang et al.121
HC due to charging. However, aer the 7th cycle, as seen in synthesized spherical nanoparticles of Sb2S3 using a simple
Fig. 12 (a) Measured and calculated charge–discharge voltage profiles of anode (Na|hard carbon) and cathode (Na|seawater) half and full cells
(HC|seawater). (b) Charge–discharge voltage profiles of a rechargeable SWB full cell (HC|seawater) based on carbon paper and porous car-
bon@carbon paper and their obtained voltage gap. (c) Cycle performance of a rechargeable SWB full cell based on porous carbon@carbon paper
at 0.05 mA cm2. (d) Charge–discharge voltage profiles of a P/C composite anode using a rechargeable SWB full cell (P/C composite|seawater).
(e) Capacity retention of the rechargeable SWB full cell (P/C composite|seawater) operated with the P/C composite anode. (a) Reproduced with
permission.25 Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b and c) Reproduced with permission.57 Copyright 2018, Royal
Society of Chemistry. (d and e) Reproduced with permission.123 Copyright 2018, Royal Society of Chemistry.
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solution process at room temperature. In the full cell It can be commonly seen with all the studied anode mate-
rechargeable SWB, the results showed a specic capacity of rials that during the rst or rst few cycles, a low discharge
233 mA h g1 in the rst cycle which reached 485 mA h g1 at capacity with low coulombic efficiency was obtained which is
the 70th cycle. These results were obtained under the testing attributed to SEI formation. The SEI layer is usually formed by
conditions of capacity cut-off at 550 mA h g1 during charging the decomposition of electrolytes with the consumption of Na
and a voltage cut-off with 0.4 V on discharge (current density ions, thus leading to the low capacity during the rst or rst few
was 0.05 mA cm2). cycles. However, rechargeable SWB systems are an open system
The Sn-based anode has a theoretical capacity of that can supply unlimited Na ions from the seawater cathode.
847 mA h g1, based on the full sodiation state of Na15Sn4.131 Hence, in the following cycles, it is possible to compensate for
The P-based anode has a theoretical capacity of 2596 mA h g1 the Na ions consumed on the anode for SEI layer formation and
based on the formation of Na3P.131 Both are known to be cheap thereby achieve better cycling stability.
and abundant materials. However, both greatly suffer from 5.4.2. Nonaqueous electrolytes. The ideal non-aqueous
volume changes and poor electrical conductivity. Therefore, electrolyte for the rechargeable SWB anodes should have (i)
using carbon-conducting techniques such as carbon coating high stability over the operating voltage (in the low and high
and/or formation of composites with a 2D or 3D carbon matrix voltage regions), (ii) should not hinder the Na-ion transfer
are a very benecial way to buffer the volume changes and kinetics and (iii) should not damage the structure of the anode
create electric conducting pathways. Hence, J. K. Kim122 and Y. materials or react with the anode. Therefore, it is essential to
Kim123 prepared an Sn/C composite by carbonizing a SnO2/ use an appropriate electrolyte for the respective anode mate-
carbon132 compound and P/C composite by mixing P and carbon rials. Mostly, all non-aqueous electrolytes used for sodium
nanoparticles using a ball-milling method.123 These carbon batteries can be employed for the anode of a rechargeable SWB,
composites for Sn and P not only act as a conductive matrix but likely 1 M NaClO4 in EC/PC (EC stands for ethylene carbonate
also as a buffer to control the volume changes. As a result, Sn/C and PC for propylene carbonate). However, in the comparative
anodes used in a full cell rechargeable SWB exhibit a discharge study, it was found that 1 M NaCF3SO3 in a TEGDME (tetra-
capacity of approximately 300 mA h g1 (0.05 mA cm2) over 30 ethylene glycol dimethyl ether) electrolyte for hard carbon
cycles. Fig. 12d and e display the charge–discharge prole and anodes in a rechargeable SWB exhibited a better capacity for
the relative cycle performance of a full cell rechargeable SWB reversibility (Fig. 13a) and cycling stability performance with
that used P/C as an anode. Interestingly, in the rst cycle, a capacity retention of 90% over 100 cycles (Fig. 13b) compared
a discharge capacity of 700 mA h g1 with a coulombic effi- to 1 M NaClO4 in EC/PC.133 It is found that 1 M NaClO4 in an EC–
ciency of 70% was achieved and aer a few cycles, over PC electrolyte exhibits poor stability cycle performance from the
950 mA h g1 was obtained with coulombic efficiencies of 90– 30th cycle. The reason is that 1 M NaCF3SO3 in a TEGDME
96%, which was retained even aer 80 cycles (see Fig. 12e). The electrolyte supports the formation of a thin and stable SEI layer
low reversible capacity with low coulombic efficiency in the rst on hard carbon compared to 1 M NaClO4 in EC–PC.133
cycle is due to the formation of an SEI layer in the P/C anode and Ionic liquid electrolytes are well known for their excellent
the increase of capacity aer a few cycles caused a gradual electrochemical and thermal stability. The appropriateness of
activation of the PC composite. The stable high reversible different ionic liquids as an electrolyte for Sn/C and hard carbon
capacity implies the stability of the formed SEI layer on P/C and anodes in rechargeable SWBs has been studied by J. K. Kim122
structural rearrangement of P/C within the rst cycles. and Y. Kim,81 respectively. NaTFSI/Pyr14TFSI (1 : 9) ionic liquid
electrolyte with an Sn/C anode in a rechargeable SWB showed
Fig. 13 (a) Charge–discharge voltage profile and (b) cycling performance of rechargeable SWB cells (HC|seawater) with 1 M NaClO4 in EC/PC
and 1 M NaCF3SO3 in TEGDME electrolytes at 0.05 mA cm2. (c) Comparison of cycling performance of rechargeable SWB cells (HC|seawater)
with NaFSI–Py13FSI–Py13TFSI electrolyte and 1 M NaCF3SO3 in TEGDME electrolyte. Herein, Pyr13FSI stands for N-methyl-N-propylpyrrolidinium
bis(fluorosulfonyl)imide; Pyr13TFSI stands for N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide and NaFSI stands for sodium
bis(fluorosulfonyl)imide. (a and b) Reproduced with permission.133 Copyright 2018, Royal Society of Chemistry. (c) Adopted with permission.81
Copyright 2017, Elsevier.
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stable cycle performance over 50 cycles.122 Concurrently, 1 M collected scientic and methodological knowledge. Develop-
NaClO4 in EC/PC electrolyte lost its stability within 30 cycles. On ment related to cell components such as Na-ion-conducting
the other hand, impressive reversible capacity, energy effi- membranes, current collectors, anodes, electrolytes for an
ciency, and capacity retention were attained when the synthe- anode, electrocatalysts, and assembly/processing steps has
sized quaternary ionic liquid composed of Pyr13FSI (0.6 M ratio), been conducted accordingly. Our coin cell designs can be used
Pyr13TFSI (0.3 M ratio), and NaFSI salt (0.1 M ratio) with 5 wt% only for lab purposes and cannot be used for real application.
EC additive as a liquid electrolyte was combined within a hard Therefore, the prismatic cell has been designed for practical
carbon anode in a rechargeable SWB.81 As shown in Fig. 13c, application purposes through appropriate engineering. Fig. 14a
this ionic liquid electrolyte allowed the hard carbon (derived displays the fabricated prismatic cells with and without cathode
from peanut shells) anode used in a rechargeable SWB to ach- current collectors (i.e. carbon cloth). These prismatic cells are
ieve a stable cyclability with a high energy efficiency of 80–85% the thinnest and lightest so they can offer a smaller space
over 300 cycles, but the same HC-based rechargeable SWB with utilization when being used in large scale application as well as
1 M NaCF3SO3 (in TEGDME) electrolyte displayed an ambiguous have the potential for larger capacity and higher electrical
decrease in energy efficiency aer 150 cycles. energy storage. Square-type NASICON ceramics with 24
Using nonaqueous electrolyte and anode electrode materials numbers (12 per side) are used in this prismatic cell. Fig. 14b
separately in the anode side of the rechargeable SWBs could shows the prototype module which is composed of 40 prismatic
increase the total cost of the system. In this regard, we are cells. Recently, assembling several prototype modules
attempting to utilize a sodium polycyclic aromatic hydro- (composed of 2000 cells) in a rack as shown in Fig. 14c, we have
carbon134 based semi-liquid as an anode, for instance, sodium reached 10 kW h. The obtained galvanostatic charge–discharge
biphenyl.135,136 The merit of this kind of semiliquid anode is that and power performance results of the unit cell and stacked cells
it can behave as an electrolyte as well unlike conventional (in parallel) are shown in Fig. 14d and e. From this result, it can
anodes (hard carbon, Sb2S3, Sn/C, P/C, etc.).22 Consequently, we be determined that when the number of cells in a stack
are expecting that the successful employment of sodium poly- increases, the voltage gap decreases (for tests of 5 hours) and
cyclic aromatic hydrocarbon based semi-liquid as an anode will power output increases.25
reduce the cost of rechargeable SWBs for their
commercialization.
7. Application of rechargeable SWBs
6. Prismatic cell design and cell stack Rechargeable SWBs can be operated as an open cathode system
where the charge and discharge processes are completed in
We have developed coin cell platforms and ow-type cell testers seawater as a cathode. Therefore, it is expected that these
over the past few years (see Section 5.1) through which we have rechargeable SWBs are more suitable for the marine sector,
Fig. 14 Schematic illustration of the development of rechargeable SWB prismatic cells for ESSs. (a) Anode part of the unit cell (Ver. 1) and
complete unit cell (Ver. 2). (b) A module of rechargeable SWB that comprises 40 prismatic cells. (c) Arrangement of several modules in a rack that
contains 2000 prismatic (rechargeable SWB) cells. (d) Charge–discharge voltage profiles of the unit cell, 3 cell stack and 5 cell stack rechargeable
SWBs operated at a current of 30 mA. (e) Polarisation curves of the unit cell, 3 cell stack and 5 cell stack rechargeable SWBs plotted at a scan rate
of 0.04 mA s1 per unit cell. (d and e) Adopted with permission.25 Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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offshore and seaside power sources, or energy storage applica- maintenance-free option. Hence, it is possible to replace lead-
tions. The possible applications of rechargeable SWBs are acid batteries with rechargeable SWBs.
illustrated in Fig. 15. Our expected applications for rechargeable
SWBs are described briey as follows.
7.3. Autonomous surface vehicles (ASVs)
ASVs are similar to oating equipment on seawater like a light
7.1. Life jackets
buoy. They are used to evaluate the water depth and detect
For life jacket applications, the battery should provide instant obstructions using ultrasonic signals for ships and boats. Most
power necessary to activate mounted GPSs and light sources. ASVs are deployed in ports and harbors. RSWBs can store the
Likely, the anode part of this rechargeable SWB is completely power from solar panels and provide a non-stop power supply to
isolated from the cathode so when its cathode part comes into provide 24 hours of operation on the water surface.
contact with seawater, it can start to provide instant power.
Therefore, marine life jackets could use this type of SWB (in the
7.4. Underwater robots, drones, and scooters
charged state) to power a light source and operate a GPS
attached to the jackets. The light and GPS can provide the Underwater robots and drones are also called remotely operated
positioning of a person who needs help in emergencies,11 for vehicles (ROVs) which are used in the military and heavy
example, during a shipwreck or when a boat capsizes. industries like oil extraction companies. They are also used for
oceanographic research to study marine life and their difficul-
ties. Underwater scooters (UWSs) are used for tour purposes for
7.2. Light buoys
viewing colorful sh and intricate reefs inside the oceans.
The light buoy is a kind of object like a lighthouse which is also However, all of these are operated by an electrical power supply
used in the sea/ocean as navigational equipment or warning of batteries, so these rechargeable SWBs can be a good candi-
points about obstructions for ships and boats. Present light date to be adopted as a power source in ROVs and UWSs.
buoys mostly use toxic, poor energy density, and heavy lead-acid
batteries to power the mounted LED lights, GPS, and moni-
7.5. Offshore and seaside energy storage
toring systems (used for monitoring water temperature,
current/wind speed and direction, and water salinity). Nearly 50% of the world's population lives near the sea. Of the
Compared to lead-acid batteries, rechargeable SWBs can 17 largest cities in the world, 14 are located near coasts, and
provide a high energy density, eco-friendly, low weight, and they consume the majority of electrical energy. The required
electrical power transferred from a long distance increases costs
and reduces energy efficiency. Recently, renewable energy
technologies such as solar, wind, wave, and tidal-based energy
generators have been deployed offshore and on the seaside to
minimize energy transmission distances. However, a large-scale
EES system is necessary to supply stable electrical energy and
rechargeable SWBs can be a much better option for electrical
energy storage in huge quantities. It is expected that the
offshore and seaside deployment of rechargeable SWBs could
be very easy as they operate in seawater as main battery
components.
Herein it must be noted that the application of rechargeable
SWBs is not limited only to applications shown in Fig. 15 but
can also be extended to other applications.
8. Extended concept for

rechargeable SWBs
Considering the unique features of rechargeable SWBs such as
the cathode open structure for different possible cathode elec-
trochemical processes and sodium harvesting (or removal) from
seawater and their advanced cell design, it was expected that
there is a great opportunity to extend their concept for seawater
Fig. 15 Possible potential applications for the rechargeable SWBs. desalination, CO2 capture, photo-charging of SWBs, H2
Power sources for life jackets, power buoys, automatic surface vehi-
production and seawater disinfection without losing their
cles (example: sonar sensors for depth calibration), underwater vehi-
cles (example: robots, drones and scooters). ESSs for wave/tidal energy storage characteristics. Some of the reported proof-of-
energy and offshore energy islands that comprise solar panels and concept studies for the extended rechargeable SWB concept
wind turbines. are described below.
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8.1. Seawater battery (SWB)-desalination system Table 2 Ion concentration of seawater before and after the 10th
charging. Reproduced with permission from ref. 137. Copyright 2018,
As can be observed above, during the charging process, the Na+ Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ions move from seawater to the anode and the moved Na+ ions
are isolated by NASICON from seawater. Therefore, if we could Ion concentration (mg L1)
modify the cathode side of a rechargeable SWB to (re)move
Sample Na+ Mg2+ K+ Ca2+ Cl SO42 Total
chloride ions, we can expect the function of desalination to be
achieved. Therefore, a rechargeable SWB can be modied into Pristine seawater 10 166 1229 395 450 19 916 2754 34 910
a SWB-desalination system, as shown in Fig. 16a. This proof-of- Aer the 10th charge 9072 1171 369 429 18 176 2681 31 898
concept of the SWB-desalination system contains137 four
compartments which are charge cathode, desalination, anode,
and discharge cathode parts. The desalination compartment is decreased, as shown in Table 2. Moreover, the pH value of water
separated from the charge cathode compartment at the le side in the charge cathode compartment increases due to the
by an anion exchange membrane (AEM) and anode compartment formation of H+ ions through the OER (Fig. 16c). On the other
at the right side by NASICON, respectively. NASICON is also used hand, with increasing discharge cycles, the pH value of water in
to separate the anode from the discharge cathode compartment. the discharge cathode compartment rises due to the creation of
Fig. 16b shows the charge and discharge capacity and the OH ions via the ORR (Fig. 16d). Therefore, this proposed proof-
coulombic and energy efficiency of SWB desalination systems of-concept SWB-desalination system can not only store/deliver
(from the 2nd cycle). During charging of the system, Na+ ions electricity and desalination, but can also produce an acid–
move to the anode side, and simultaneously Cl ions transfer to alkali solution.
the charge cathode compartment and form HCl solution by
electrochemical reaction with water. During discharging of the
8.2. Seawater battery-desalination carbon capture (SWB-DC)
system, NaOH solution is formed in the discharge cathode
system
compartment by the electrochemical reaction of Na+ ions
transported from the anode side with water and dissolved The SWB-DC system is also a modied system of rechargeable
oxygen. Aer 10 individual charging cycles, the concentration of SWBs and operated in a very similar manner to the SWB-
Na+ and Cl ions of seawater in the desalination compartment desalination system.138 As shown in Fig. 17a, the SWB-DC
system is comprised of three main sections: (i) desalination,
(ii) anode, and (iii) discharge cathode (carbon-capture). NASI-
CON separates the anode section from the desalination and
discharge cathode sections. In this system, the charging process
completes the desalination where Cl ions and Na+ ions from
seawater are removed by Cl capture using an Ag (foil) cathode
and Na+ harvesting at the anode, respectively (eqn (4) and (5)).
The discharge process completes the carbon-capture with the
assistance of NaOH which forms during the ORR. This carbon
capture process can occur through the reaction between NaOH
and CO2 (eqn (6)) and a metal hydroxide (for instance, Ca(OH)2
or Mg(OH)2) and CO2 (eqn (7)) where Ca(OH)2 and Mg(OH)2 can
be formed via a reaction between Ca2+, Mg2+, and NaOH in
seawater (eqn (8)).138
During charge:
Na+ + e / Na (4)
Ag (s) + Cl (aq) / AgCl (s) + e (5)
During discharge:
2NaOH (aq) + CO2 (g) / Na2CO3 (aq) + H2O (l) (6)
M(OH)2 (aq) + 2CO2 (g) / MCO3 (aq) + H2O (l);

M ¼ Mg or Ca (7)
Fig. 16 (a) Schematic diagram of the designed SWB-desalination
system and its possible charge and discharge process. (b) Charge and
Metal hydroxide formation (Ca(OH)2 and Mg(OH)2) in
discharge capacities and the corresponding coulombic efficiency of
the SWB-desalination system for ten cycles at 10 mA g1. The pH seawater:
change with cycle number during charge (c) and discharge (d). (a–d)
Reproduced with permission.137 Copyright 2018, Wiley-VCH Verlag 2NaOH (aq) + MCl2 (aq) / 2NaCl (aq) + M(OH)2 (aq);
GmbH & Co. KGaA. M ¼ Mg or Ca (8)
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reduce the cost of the system, and (ii) an open cathode struc-
ture, thus allowing a supply of fresh seawater for unlimited
electrical energy storage in the form of Na+ ion storage. Also, the
ow of fresh seawater through the open cathode structure can
diminish the heating problem of the battery system. More
importantly, there are several possible applications identied
for SWBs where they could act as a potential power provider or
ESS. In this review, we introduced in detail the structure and
chemistry of SWBs, ongoing academic research, and R&D
progress to achieve high-performance rechargeable SWBs in
terms of cathode current collectors, electrocatalysts, solid
electrolytes, anodes, and non-aqueous electrolytes for the

anode. In contrast, the relevant fundamental studies and
technologies are still in their early stages; thus, rechargeable
SWBs need further R&D before commercialization.
10. Challenges and future directions

Through this review, we have identied several challenges that
need to be studied and solved, both fundamentally and tech-
Fig. 17 (a) Schematic illustration of the designed SWB-DC system and
nically, for SWBs as listed below.
its charge and discharge process. (b) Change of CO2 concentration (i) Currently, the OER and ORR are reported as an expected
with time at 0.1 and 1 mA cm2. (c) XRD patterns of the collected cathodic reaction, but along with the OER, practical reactions
powders after the discharge process (0.1 mA cm2) using distilled like the HCFR or chlorine evolution reaction can perhaps occur
water and NaOH (aq) of various concentrations (0.01–1 M) for CO2 when these SWBs are operated at high currents due to the
capture. The inset shows the powder obtained from the distilled water
after the discharge process. (a–c) Reproduced with permission.138
sluggish kinetics of the OER process. To assess this conse-
Copyright 2019, Elsevier. quence, an in situ/ex situ quantitative analysis will need to be
conducted in future research.
(ii) There are several electrocatalysts which have been
Na+ and Cl ion concentrations in seawater changed with studied on cathode current collectors to elevate the OER/ORR
charging time at different current densities (0.1 to 0.5 mA cm2) process to reduce the voltage gap or improve the voltage effi-
where the ion (Na+ and Cl) concentration decreased with time, ciency of SWBs (see Section 5.3). While studying the feasibility
and elevated current density encouraged the quick reduction of of electrocatalysts in SWBs, it was noted that aer a few cycles,
ion (Na+ and Cl) concentration with time (not shown; for voltage gaps had been increased. Unfortunately, the reason
details see ref. 138). As a result, there was a decrease of 3.3% Na+ behind this was not identied. This voltage gap increases aer
and 8.3% Cl at 0.1 mA cm2, and 19.9% Na+ and 20.4% Cl at 1 some cycles and could have arisen from either instability of the
mA cm2.138 Moreover, it was conrmed that the concentration anode/non-aqueous electrolyte or the degradation of the elec-
of CO2 decreased with charging time (see Fig. 17b). The XRD trocatalyst or cathode current collector during the OER and
results, as shown in Fig. 17c, validate the reaction between ORR processes; thus a systematic investigation is required for
NaOH and CO2 and their product of sodium (bi)carbonates. verication. Carbon and carbon cloth are currently used as low-
CaCO3 formation was also conrmed using XRD results (not cost and stable cathode collectors in seawater cathodes but
shown; for details see ref. 138), which conrms the CO2 reaction studies comparing their stability with other cathode current
with Ca(OH)2 where MgCO3 was not formed because CaCO3 collectors are still lacking.
formation is thermodynamically favored over MgCO3 formation (iii) The pH of seawater near the cathode current collector
in seawater. This modied rechargeable SWB system provides does not need to be similar during the charge/discharge process
a great way to carry out desalination and carbon-capture and can change. This pH change could affect cell components
together using a single system. or cell performance indirectly. For example, alkalization during
the ORR process can encourage the formation or precipitation
of insoluble salts of magnesium and calcium (Mg(OH)2 and
9. Summary CaCO3/CaSO4) on the current collector, which will signicantly
disturb the operation of this battery system and output voltage.
The search for low-cost and environmentally friendly battery On the other hand, seawater not only contains several dissolved
systems with reasonable energy and power density has revealed salt ions (Na+, K+, Mg2+, Ca2+, etc.) but also microorganisms and
several new battery chemistries in recent decades. In this line, algae. The microorganisms and algae can accumulate or grow
the development of rechargeable SWBs as a new battery system naturally (i.e. biofouling), which can harm the overall battery
has attracted signicant interest due to their ideal merits: (i) use system and reduce the life of the battery system. Hence, the
of abundant seawater as a cathode, which can signicantly inuence of insoluble salt formations, and microorganism and
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algae accumulation on rechargeable SWB components can (vii) Expensive titanium frames are usually used as an elec-
affect the performance and lifetime of battery systems, which trical lead in SWB packs. In further studies, graphite frames will
will be examined through elaborate systematic studies. be designed and considered as an alternative to titanium.
(iv) The current SWB battery performs well only at low We hope the proposed future research directions can further
current densities due to high resistance associated with accelerate the research progress of rechargeable SWBs toward
NASICON solid electrolytes, which results in low power its commercialization.
performance. Consequently, ionic conductivity needs to be
improved from 1 103 S cm1, and the thickness must be Conflicts of interest
reduced to attain rechargeable SWBs with reasonable power
performance. Introducing foreign atoms by replacing Na or Zr There are no conicts to declare.
or excess Na in NASICON could help to improve the conduc-
tivity. The electrochemical stability of NASICON against Acknowledgements

seawater and non-aqueous electrolytes has been tested for
a small number of cycles, which is not enough to assess its This work was supported by the 2019 Research Fund
potential; therefore, a long cycle performance study with (1.190006.01) of the Ulsan National Institute of Science and
testing for more than 1000 cycles with a duration of 6 months Technology (UNIST), and Research Fund of KEPCO (R17EH03).
is highly desired. Similarly, NASICON acts a separator for the This research was further supported by the Korea Research
non-aqueous electrolytes and seawater so it must have enough Fellowship Program through the National Research Foundation
mechanical stability to keep them always away from each of Korea (NRF) funded by the Ministry of Science and ICT
other. In this sense, the mechanical stability of NASICON (2016H1D3A1909680). We thank Young Jin Kim, Jinho Lee and
during cell fabrication and assembly must be studied. Partic- Young Jae Jung for the preparation and arrangements of gures.
ularly, the cost-effectiveness of NASICON must be conrmed
for its mass production. References
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Journal of

Emergence of rechargeable seawater batteries

At present, rechargeable Li-ion batteries (LIBs) are the most

Journal of Materials Chemistry A Review

competitive features. Compared with LIBs, however, the

2. Seawater 3. History: development of SWBs

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

(intercalation/deintercalation and OER/ORR); however, still

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

8. Extended concept for

Journal of Materials Chemistry A Review

Ag (s) + Cl (aq) / AgCl (s) + e (5)

2NaOH (aq) + CO2 (g) / Na2CO3 (aq) + H2O (l) (6)

M(OH)2 (aq) + 2CO2 (g) / MCO3 (aq) + H2O (l);

Review Journal of Materials Chemistry A

electrolytes, anodes, and non-aqueous electrolytes for the

10. Challenges and future directions

Journal of Materials Chemistry A Review

tivity. The electrochemical stability of NASICON against Acknowledgements

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

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